The Multi-scale Multi-functional Materials Group (M3) is a multidisciplinary team interested in materials whose exploitable physical properties are linked to a complex and more or less hierarchical structuring from the atomic to the micrometric scale. The materials studied are the opposite of fractal structures, in the sense that their characterization at a given scale does not predict their structures at higher or lower scales.
The most emblematic materials are composite materials, which can range from their simplest expression (nanoparticles in a matrix) to more complex configurations (nano-objects grouped in aggregates and dispersed in an anisotropic matrix). The multifunctional character comes from the simultaneous exploitation of several properties resulting from the multiscale character of the same material. It can also concern a class of materials whose controlled variations in structuring make it possible to cover a broad spectrum of applications.
Currently three themes with societal stakes are developed in the group. The first one concerns carbon and its versatility at the nanometric scale, the second one concerns the elaboration of multifunctional nanoparticles for medical imaging and the last one concerns the study of ancient materials with partially hierarchical structure and multiple functions.
Group leader: Marc Verelst
The work of the Nanocarbon team focuses on the development and applications of materials made of or containing carbon, or related materials, in particular based on reduced dimensional systems (0D to 2D). This work is valued through expertise and projects in the fields of excellence.
Such a thematic requires to solve fundamental problems (mechanisms of synthesis and behavior) as well as technological ones. For this, we may have to develop our own analytical methods: this is the first approach of our work. Indeed, thanks to its competences in Raman spectrometry, electron microscopy, X-ray diffraction, EELS analysis, near-field optics, the Nanocarbons team contributes to methodological developments in the field of diffraction or magnetic dichroism, for example, to answer particular problems. These rich approaches allow inter-group links within CEMES and the realization of prototypes (near field optics).
The following work approach concerns the materials studied, which can be divided into two categories. The first one corresponds to the continuity of our “historical” activity: In the last few years, the work on carbonization and graphitation mechanisms, the synthesis of carbon nanocones, the analysis of collapsed (flattened) carbon nanotubes, the use of graphene as a conductive electrode and carbon nanotubes as a support for catalysis, has contributed to demonstrate the richness of this theme as well as the insertion of the group in the local, national and international context. Materials made of nanocarbons combined with other types of materials (polymers in particular) in order to generate particular collective behaviors and properties are also studied.
The other category of materials focuses more specifically on 2D systems. It differs from the previous one because it started with studies of the structure and defects of graphene itself for example in order to probe the local electromagnetic field (graphene bubble) and continued with the use of graphene for the fabrication of “diamane”, but has been extended to other non-carbon 2D materials such as WS2, MoS2, and some perovskites. These studies range from compound to demonstrator. Several funded projects are underway: on diamane and the realization of a diamane/graphene device, graphene electrodes used as contact with conventional semiconductors such as silicon and perovskites with the analysis of electron-phonon coupling among others.
Finally, a last approach is to respond reactively to requests for expertise generated by our skills and emanating from both the academic and industrial worlds, leading to (1) collaborations at the local (co-tutored thesis for the use of recycled carbon blacks), national (Raman with Bordeaux and Montpellier), and international (European program on nanocomposites) levels; (2) interactions with industrialists, ranging from free advice to contractual relationships for detailed analyses based on our knowledge of materials and the tools we have developed (CARBICE, IRT, Chord Electronics, Carestream Dental) or informally within networks such as learned societies like SFEC (X-ray diffraction) and SFµ (EELS), or GDRs like HOWDI.
The different research topics of the Nanocarbon team are presented below.
Definition of three basic structural components (BSCs) and example of a perfect fit of an experimental X-ray spectrum by the model components
Thermodynamics leads all carbon materials to approach graphite. On their way to this structure, the carbonization of organic precursors initially generates sub-nanometric graphene crystallites, more or less aligned in anisotropic domains of variable sizes, which gradually combine into larger crystallites, nanometric to micrometric. Then graphitation changes the crystallographic structure of the crystallites from turbostratic to hexagonal.
But this ultimate progressive structural modification is not systematic, and many carbons, depending on the nature of their precursor, remain in the turbostratic or at most partially graphitized state. Moreover, stacking faults (rhombohedral structure) can occur, naturally or under the influence of external conditions (pressure). The mechanisms of carbonization and graphitization are therefore complex, and not fully elucidated.
In the current strategy of exploitation of X-ray diffraction, once the diffractogram is obtained experimentally, one compares positions and intensities of the peaks with the PDF (Powder Diffraction File) database of the ICDD (International Centre for Diffraction Data). Nevertheless, in the case of disordered carbon, there is no universal approach. We have calculated diffractograms from the atomic positions and generated from them ad hoc functions that allow to fit the experimental diffractograms from 3 main structural components (BSC), in a first step. This allows to have identical results for peaks 10 and 11 concerning the La (width of crystallites) as well as to know the composition of the average crystallite in terms of its proportions in basic structural components. This action is a long term work based on our skills acquired over many years.
The studies concern both graphitable carbons (such as pitch cokes) and non-graphitable carbons (such as cellulosic precursors).
Publications:
– Mubari P. K., Beguerie T., Monthioux M., Weiss-Hortala E., Nzihou A., Puech P. (2022) Specific X-Ray, Raman and TEM signatures of cellulose-derived carbons. ‘C’ 8, 4.
– Puech P., Monthioux M. (2020) A new insight on the understanding of carbonisation and graphitisation mechanisms. Indian Journal of Engineering and Material Science 27, 1095-1099
– Monthioux M. (2020) Comments on: “Structure evolution mechanism of highly ordered graphite during carbonization of cellulose nanocrystals” by Eom et al. (Carbon 150 (2019) 142-152). Carbon 160, 405-406.
– Ouzilleau P., Gheribi A. E., Chartrand P., Soucy G., Monthioux M. (2019) Pourquoi certains carbones peuvent-ils ou non se graphitiser ? Le point de vue de la thermodynamique. Carbon 149, 419-435.
– Puech P., Dabrowska A, Ratel-Ramond N., Vignoles G., Monthioux M. (2019) New insight on carbonisation and graphitisation mechanisms as obtained from a bottom-up analytical approach of X-ray diffraction patterns. Carbon 147, 602-611.
This approach is continued by calculating 2D electron diffractograms for 2D materials (less than 5 layers) and for non-graphitable materials.
Publication:
Puech, P., Gerber, I. C., Piazza, F., Monthioux, M. (2021). Combining low and high electron energy diffractions as a powerful tool for studying 2D materials. Applied Physics A, 127(6), 1-8.
Evidence, by iodine filling (white lines) of asymmetric inter-graphene decohesions in variable number (here from 1 to 4) in carbon nanotubes synthesized by electric arc plasma
Because of the variety of conformations and associations that graphenes can adopt (the same diversity as for sheets of paper), and the variety of possible defects, whether in-plane (non-hexagonal aromatic rings, with 5, 7 or 8 carbons, vacancies, free edges) or out-of-plane (stacking sequences, AAA, ABA, ABC, AA’A, turbostratic… The understanding of carbon structuring mechanisms, in particular graphenic ones, including the knowledge of the nature and location of defects, is an important issue for the control of morphologies during synthesis, and of behavior during use. A variety of work is thus carried out in a recurring way around the mechanisms of structuring, as well as the recognition of the defects, their role, and even their exploitation.
These works concern:
– The identification of specific defects and their signatures
Publications:
– The effect of pressure on the structuring and the Raman signal, based on an exemplary series of pitch cokes (graphitable organic precursor).
Publication:
Pillet G., Sapelkin A., Bacsa W., Monthioux M., Puech P. (2019) Size-controlled graphene-based materials prepared by annealing of pitch-based cokes: G band phonon line broadening effects due to high pressure, crystallite size and merging with D’ band. Journal of Raman Spectroscopy 50, 1861-1866
– The exploitation of the reactivity of defects to propose an optimized method for the purification of nanocarbons, using the principle of the slaving of the combustion temperature to the response of the thermogravimetric analysis. The method allows the specific removal of carbon phases whose respective combustion temperatures are separated by a few degrees.
Publication:
Pichaud E., Hof F., Derré A., Noé L., Monthioux M., Pénicaud A. (2022) Burn them right! Determining the optimal temperature for the purification of carbon materials by combustion ‘C’ 8, 31. (Journal cover).
– The evidence that multiwall carbon nanotubes synthesized by electric arc (thus at very high temperatures, close to 3000°C) have an asymmetric cross-section due to the effect of the anisotropy of thermal expansion coefficient which creates interplanar decoherences at cooling, all located on the same side of the nanotube. This is an unexpected discovery, considering that this type of nanotubes has been studied for 30 years.
Publication:
Torres Dias A. C., Impellizzeri A., Picheau E., Noé L., Pénicaud A., Ewels C, Monthioux M. (2022) Asymmetrical cross-sectional buckling in arc-prepared multi-wall carbon nanotubes revealed by iodine filling. ‘C’ 8, 10.
Graphene bubble on an interferential substrate and laser beam forming a standing wave. Selective heating of the bubble
The highly elastic and flexible nature of graphene allows the creation of large stable bubbles on its surface in a controlled manner. When the graphene is illuminated with a laser beam, the incident and reflected beams form an optical standing wave. Increasing the laser power selectively heats the graphene bubble at the interference maxima of the standing wave. The local temperature change can be detected by following the Raman spectral shifts. Heat flow modeling allows to deduce the thermal conductivity of graphene and elastic properties of graphene at high temperatures. (Collaboration with South Korea, RS Ruoff, IBS, NanoX support).
Publication:
Huang Y., Wang X., Zhang X., Chen X., Li B., Wang B., Huang M., Zhu C., Zhang X., Bacsa W. S., Ding F., Ruoff R. S. Raman spectral band oscillations in large graphene bubbles. Phys. Rev. Lett. 120, 186104 (2018)
Raman spectrum with Stokes and Anti-Stokes parts showing oscillations related to the presence of polarons in the range 100-300 cm-1 during resonant excitation on the fundamental gap
Perovskites are soft materials with remarkable optical properties of absorption and emission, having led to solar cells with an efficiency of 25%. These properties are linked to the presence of polarons, i.e. electrons surrounded by a deformation of the crystal lattice, which we study in detail.
The expertise of the team in Raman spectrometry and the set of equipments available at CEMES, ranging from UV to infrared with also a spectrometer with TERS application (Tip Enhanced Raman Spectroscopy) and the possibility to analyze low frequencies (10-100 cm-1 area) allowed us over the years to move from simple characterization to the search for specific signals at electron-phonon couplings. First in collaboration with KU-Leuven and now also with the LNCMI (Toulouse), we analyze under specific conditions Raman spectra (temperature and wavelength scanning) to understand the coupling between electrons and lattice, both in 3D and 2D perovskites.
Publication:
Steele J. A., Puech P., Monserrat B., Wu B., Yang R. X., Kirchartz T., Yuan H., Fleury G., Giovanni D., Fron E., Keshavarz M., Debroye E., Zhou G., Sum T. C., Walsh A., Hofkens, Roeffaers, M. B. J. (2019). Role of electron–phonon coupling in the thermal evolution of bulk rashba-like spin-split lead halide perovskites exhibiting dual-band photoluminescence. ACS Energy Letters, 4(9), 2205-2212.
Structure of diamane (C = blue; gray = H), and Raman spectrum of a bilayer graphene before (blue) and after (red) hydrogenation
The conversion of a graphene bilayer formed from sp2-hybridized carbon by hydrogenation to diamane, i.e., sp3-hybridized carbon. This material is new in the 2D family and presents exceptional thermal transport properties. It is an electrical insulator, with an electronic gap of about 4 eV.
This theme started at CEMES in 2016 and continues in the framework of the ANR GLADIATOR project, including LPCNO (INSA Toulouse), ISM (Bordeaux), UBC (Vancouver, Canada) and PUCMM (Santiago, Dominican Republic). Our objective is to fabricate planar electronic devices with conductive C-sp2 areas and areas converted by hydrogenation to dielectric C-sp3.
Our leadership in this rapidly growing international field is beginning to be recognized, and has earned us an invitation to edit a special issue of the Journal of Carbon Research ‘C’. It is also one of the axes of the CNRS International Research Project (IRP) NEWCA between France and Dominican Republic.
Publications:
Schematic of the mechanism of pyrolytic carbon deposition by ToF-CVD on carbon nanotube, resulting in the formation of carbon nanocones
The work we have been doing for years around the synthesis of carbon nanocones by a particular CVD synthesis process called “time of flight” has made great progress thanks to the thesis of G. Paredes (defended in October 2020). Due to the fact that this synthesis involves depositing pyrolytic carbon on individual carbon nanotubes as a formation and growth medium, the knowledge of the general mechanisms of carbon deposition by CVD in their early stages has made significant progress. In particular, the work validated the existence, proposed since the 1950s but still controversial, of a transient liquid organic phase, even at 1400°C, which condenses on the deposition support (here the nanotubes) from the species generated by thermal cracking. It is the behavior of this liquid phase guided by the wetting mechanisms of a nanoscale wire, which take place in a few microseconds, that is essentially responsible for the conical shape of the obtained carbonaceous solid. The work has been noticed and has earned an invitation to present it in a plenary conference at the World conference on Carbon CARBON-2022 (London).
Publications:
– Paredes G., Wang R., Puech P., Seine G., Leyssale J.-M., Arenal R., Masseboeuf A., Piazza F. Monthioux M. (2022) Texture, nanotexture, and structure of carbon nanotube-supported carbon cones. ACS nano (in press).
– Paredes G., Ondarçuhu T., Monthioux M., Piazza F. (2021) Unveiling the existence and role of a liquid phase in a high temperature (1400 °C) pyrolytic carbon deposition process. Carbon Trends 5, 10017.
The work continues with the exploitation of the remarkable geometrical and physical characteristics of carbon nanocones as probes for near-field microscopies.
Publication:
Paredes G., Seine G., Cours R., Houdellier F., Allouche H., Ondarçuhu T., Piazza F., Monthioux M. (2020) Synthesis and (some) applications of carbon-nanotube-supported pyrolytic carbon nanocones. Indian Journal of Engineering and Material Science 27, 1091-1094.
This topic is the second thematic component of the NEWCA IRP.
Identification, by electron energy loss spectroscopy (EELS), of a molybdenum oxychloride phase partially filling a single-walled carbon nanotube, and of the chlorination of the tube
The term “nano-composite” is most often applied to a material made of several components, one of which has at least one nanometric dimension. Typically, it is a matrix (polymer, ceramic, metal) in which is dispersed a charge (carbon nanotubes, graphenes, carbon blacks, fullerenes). However, in its strict sense, it refers to nanometric objects whose composite character is also at the nanometric scale. A typical example is the filling of the cavity of carbon nanotubes by atoms, molecules, nanoparticles and non-carbon phases. This is a recurrent work in the team, since it was one of the first two in the world to reveal, in 1998, the possibility of inserting molecules in the cavity of single-walled carbon nanotubes. Recent work has involved the identification of the filling mechanisms associated with a new synthesis method at room temperature using the dissociating effect of UV radiation, as well as the demonstration that a quasi-integral filling of the cavity of wall carbon nanotubes with iodine or water increases their mechanical compressive strength by up to a factor of 2.
Publications:
– Bousige C., Stolz A., Silva-Santos S. D., Shi J., Cui W., Nie C., Marques M. A. L., Flahaut E., Monthioux M., San-Miguel A. (2021) Superior carbon nanotube stability by molecular filling: a single-chiral study at extreme pressures. Carbon 183, 884-892.
– Mittal J., Monthioux M., Serin V. (2019) Photolysis-driven, room temperature filling of single-wall carbon nanotubes. Journal of Nanoscience and Nanotechnology 19, 4129-4135
NanoDESK (2017-2020) has developed web-based tools to help companies use nanocomponents in composites. This is a European funded Interreg action to promote investment in nanotechnology in Southern Europe in a safe and sustainable way in the plastics sector, solving current barriers by developing a set of tools to help companies make decisions. Outputs include a collection of web-based tools, providing applications to identify nanofillers (including carbon nanotubes and graphene) for targeted applications, advanced browsers to improve access to related information or online characterization of toxicological profile and exposure potential of relevant nanomaterials.
Partners included: Faculdade de Ciencias, Universidade do Porto (FCUP), Portugal; Iberian International Laboratory of Nanotechnology (INL), Portugal; Instituto Valenciano Seguridad y Salud Trabajo (Invassat), Spain; Instituto Tecnológico del Embalaje, Transporte y Logística (ITENE), Spain; ProtoQSAR, Spain, for the development and application of computerized methods for the evaluation of physicochemical, biological and/or (eco)toxicological properties of chemicals, of natural or synthesized origin; Universitat Rovira i Virgili (URV), Spain, CEMES, through our group, for the expertise in characterization.
EDS elemental analysis in an electron microscope of recovered carbon blacks and silica
Through an action between the Ecole des Mines d’Albi and the CEMES supported by the region via a thesis grant, we are characterizing the differences between the original N300 carbon blacks and those obtained after recycling the tires by a vapothermolysis process. The CEMES, with its numerous equipments (Raman, TEM, Zeta, DLS, X-rays, transmission) and expertise in the field of carbons, brings numerous tracks which are explored to reuse the carbon blacks, either in the original application (which is the target of the tire manufacturers), or in applications of type electrodes.
Exaltation of the optical field in a graphene/SOI junction thanks to the formation of a standing wave. Comparison with and without SIO2 layer tuned to the wavelength
Studies on the role of optical interference on the performance of the ultra-thin Si/graphene solar cell. The goal is to reduce the thickness of the crystalline Si layer to make the Si layer optically transparent and reduce the reflection loss. Realization of the cell and modeling of the optical field.
(NanoX project in progress, in collaboration with SINano-CEMES and MEM-CEMES)
Difference in the distribution of platinum nanoparticles on carbon nanotubes for a polymer or taking graphene oxide
Raman spectroscopy and electron microscopy studies of modified carbon nanotubes as a support for platinum particles, in order to improve the oxygen reduction reaction in a fuel cell (in collaboration with IIT Madras, India, CEFIPRA project).
Publications:
– Garapati M. S., Nechiyil D., Joulié S., Bacsa R. R., Sundara R., Bacsa W. (2022) Proton-Conducting Polymer Wrapped Cathode Catalyst for Enhancing Triple-Phase Boundaries in Proton Exchange Membrane Fuel Cells. ACS Appl. En. Mater. 5(1), 627-638. https://doi.org/10.1021/acsaem.1c03143
– Nechiyil D., Garapati M. S., Shende R. C., Joulié S., Neumeyer D., Bacsa R., Puech P., Ramaprabhu S., Bacsa W. (2020) Optimizing metal-support interphase for efficient fuel cell oxygen reduction reaction catalyst. Journal of Colloid and Interface Science 561, 439-448. doi.org/10.1016/j.jcis.2019.11.015
Optical standing wave near a surface and optical probe. Standing wave parallel or perpendicular to the surface using one or two incident beams
Near-surface and nanoscale optical field imaging can be used to improve spatial resolution. Diffraction and optical interference near surfaces leads to interference bangs. A digital reconstruction of the surface image is implemented. Realization of an interference microscope and development of holographic reconstruction in intermediate field (NanoX project).
Publication:
Bacsa W., Bacsa R., Tim M. (2020) Optics Near Surfaces and at the Nanometer Scale. Springer Briefs in Physics. ISSN: 2191-5423.
Schematic of the method of transferring carbon nanotube layers and forming a composite on the polymer surface
The conductivity of thermoplastic polymers can be improved by using conductive fillers on the surfaces. Carbon nanotubes are incorporated into a thermoplastic poly(ether ether ketone) (PEEK) polymer by annealing uniform thin layers of carbon nanotubes onto the polymer surface. Carbon nanotube thin films of 2 cm2 surface area were obtained from suspensions of nanotubes in methanol. The resulting 200 nm thick composite layers showed electrical conductivity up to 8 S/cm.
Publication:
Embedded carbon nanotubes on surface of thermoplastic poly(ether ether ketone) G. Pillet, P. Puech, S. Moyano, F. Neumayer, W. Bacsa, Polymer 226 (2021) 123807
Participants: Robert Mauricot, Marc Verelst
PhD students: Fernanda Heidiger Borges
The Nanomaterials and Processes research team develops its expertise from the most fundamental research in the field of synthesis and characterization of multifunctional nanoparticles to their valorization and societal diffusion through the creation of startups.
At the turn of the 2000s, the team developed a process for the elaboration of luminescent micro- and nanoparticles by aerosol pyrolysis in partnership with the startup DGtech and the French television manufacturer Thomson Plasma. Unfortunately, these two companies filed for bankruptcy in 2006 and 2007 respectively. Consequently, to finalize the valorization of all the work accomplished, the team actively participated in the creation of the spin off PYLOTE (clickable link: https://pylote.com/) in 2008, which developed the aerosol pyrolysis process to an industrial stage. Currently, the company PYLOTE, in partnership with CEMES, is experiencing a strong development for the manufacture and distribution of antibacterial and antiSARS-COV2 products.
Video on Youtube : https://youtu.be/WcYdOyJTOpM
Article in La Dépêche : https://www.ladepeche.fr/2021/02/16/pylote-dans-les-masques-anti-covid-9375841.php
Article in Usine Nouvelle : https://www.usinenouvelle.com/article/berry-global-choisit-la-technologie-de-pylote-pour-son-compte-goutte-ophtalmique.N1791707
Pre-industrial prototype of the aerosol pyrolysis process developed at CEMES
The collaboration between the NanoPro team and the company PYLOTE was very active from 2008 to 2012, when the team invested in another project while continuing to provide expertise and services for the company PYLOTE, which is now operating on its own.
More particularly specialized in luminescent nanoparticles based on earths, the team was at the origin of the creation, at the end of 2013, of a new spin off ChromaLys . This start-up was housed in the CEMES premises. It designed, manufactured and marketed new multimodal probes for biological, preclinical and eventually medical imaging, allowing visualization of biological processes or pathologies, in fluorescence, X-ray tomography and MRI. Unfortunately, ChromaLys filed for bankruptcy at the end of 2018 having failed to find the necessary funds to finance a clinical trial to enhance its innovations on a human clinical application for Imaging Guided Radiotherapy (IGRT).
Video on Youtube: https://www.youtube.com/watch?v=tnN_5ZfHgq8
From 2013 to 2018, the NanoPro team worked in close collaboration with the company ChromaLys with a division of tasks according to the mission of each: for the NanoPro team, the development, upstream, of new multimodal probes, innovative and ever more efficient; for the company, the rationalization of the elaboration processes, the realization of the tests in conditions of use and all aspects related to commercial development.
Diagram of a multifunctional probe for multimodal imaging
Of course, this symbiotic work has resulted in joint publications and/or joint patent applications.
Since the bankruptcy of the company ChromaLys, the team is particularly involved in the development of new luminescent probes, working in the near infrared and detectable by techniques called time gated detection, which greatly improve the signal to noise ratio both in photonic microscopy and in vivo imaging on animals.
In addition, since 2017, we have been using our expertise and experience, in collaboration with the University of Parakou, in Benin, for the synthesis and multiscale study of different depolluting materials essentially based on sands, clays or natural products. This emerging activity of the team starts from the observation of the increasing need for materials limiting the environmental impact of human activities and is part of the very broad context of sustainable development and social responsibility.
In this context, our first studies have already demonstrated the link between the nature and morphological properties of our treated materials and their ability to adsorb with good efficiency some common pollutants, especially in the treatment of agricultural effluents. Today, the aim of this research is to fully understand the mechanisms involved and to develop optimized supports for depollution that are easily achievable and totally recyclable, within the framework of an eco-responsible process.
This transverse activity is jointly led by Marc VERELST and Robert MAURICOT (M3 Group), David NEUMEYER (Characterization Platform) and Semiyou Ayélé OSSENI (University of Parakou). This is an activity that we wish to develop strongly in the future.
We are also, since 2020, coordinator of an important French-Brazilian collaboration program including 6 French laboratories and 5 Brazilian laboratories on the theme of nanothermometers. The goal of this project is to measure in-situ and 3D temperatures at a sub-micron scale for applications in biology and microfluidics. We will focus on near-infrared optical technologies using nanoparticles doped with fluorescent lanthanide ions whose emission properties are temperature sensitive. We will also study two techniques to quantify the temperature of emissive nano-objects based on ratiometric measurements or on the fluorescence lifetime. Thus, we propose to develop a tomographic (3D) imaging device allowing temperature mapping at the sub-micron scale with a sensitivity below the degree Celsius. Finally, we will also try to develop hybrid microdevices allowing both heating and temperature control at the sub-micron scale.
1- Marcela Matos, Emerson Faria, Katia Ciuffi, Lucas Rocha, Eduardo Nassar, Marc Verelst, CONCENTRATION EFFECT OF THE Eu3+ AND Bi3+ IN THE PHOTOLUMINESCENCE PROPERTIES OF YVO4 MATRIX. Química Nova, Sociedade Brasileira de Química, 2018, DOI : 10.21577/0100-4042.20170251.
2- Julien Santelli, Séverine Lechevallier, Houda Baaziz, Marine Vincent, Cyril Martinez, Robert Mauricot, Angelo Parini, Marc Verelst, Daniel Cussac, “Multimodal gadolinium oxysulfide nanoparticles: a versatile contrast agent for mesenchymal stem cell labeling.” Nanoscale, Royal Society of Chemistry, 2018, 10 (35), pp.16775 – 16786. DOI: 10.1039/C8NR03263G.
3- Sémiyou Osseni, Mathieu Masseguin, Etienne Sagbo, David Neumeyer, Jacques Kinlehounme, Marc Verelst, “Physico-chemical Characterization of Siliceous Sands from Houéyogbé in Benin Republic (West Africa): Potentialities of Use in Glass Industry.” Silicon, Springer, 2018, DOI : 10.1007/s12633-018-0022-y.
4-Freiria, GS ; Ribeiro, AL ; Verelst, M ; Nassar, EJ ; Rocha, LA «Effect of Dy3+ Amount on the Structural and Luminescence Properties of LaNbO4:Dy3+ Phosphor Obtained by One-Step Spray Pyrolysis Process” JOURNAL OF THE BRAZILIAN CHEMICAL SOCIETY, 29, 3, 594-601, MAR2018, DOI: 10.21577/0103-5053.20170172.
5- Marc Verelst, Lidia Resende Oliveira, Susane Bonamin Moscardini, Eduardo Ferreira Molina, Eduardo José Nassar, et al.. “Effect of gadolinium incorporation on the structure and luminescence properties of niobium-based materials.” Nanotechnology, Institute of Physics, 2018, 29 (23), DOI : 10.1088/1361-6528/aab83.
6- Matos, MG ; de Faria, EH ; Ciuffi, KJ ; Rocha, LA ; Nassar, EJ ; Verelst, M «CONCENTRATION EFFECT OF THE Eu3+ AND Bi3+ IN THE PHOTOLUMINESCENCE PROPERTIES OF YVO4 MATRIX.” QUIMICA NOVA, 41, 8, 849-856, AUG 2018, DOI: 10.21577/0100-4042.20170251
7- Feuillolay, C ; Haddioui, L ; Verelst, M; Furiga,; Marchin; Roques, C ; “Antimicrobial activity of metal oxide microspheres: an innovative process for homogeneous incorporation into materials” JOURNAL OF APPLIED MICROBIOLOGY, 2018, 125, 1, 45-55. DOI: 10.1111/jam.13752. In collaboration with Pylote company.
8- Phonesouk, E ; Lechevallier, S ; Ferrand, A ; Rols, MP ; Bezombes, C ; Verelst, M ; Golzio, M «Increasing Uptake of Silica Nanoparticles with Electroporation: From Cellular Characterization to Potential Applications” MATERIALS, 12, 1, 179, JAN 2019, DOI: 10.3390/ma12010179
9- Fatombi, JK ; Idohou, EA ; Osseni, SA ; Agani, I ; Neumeyer, D ; Verelst, M ; Mauricot, R ; Aminou, T «Adsorption of Indigo Carmine from Aqueous Solution by Chitosan and Chitosan/Activated Carbon Composite: Kinetics, Isotherms and Thermodynamics Studies” FIBERS AND POLYMERS, 20, 9, 1820-1832, SEP 2019, DOI: 10.1007/s12221-019-1107-y
10- Fatombi, JK ; Osseni, SA ; Idohou, EA ; Agani, I ; Neumeyer, D ; Verelst, M ; Mauricot, R ; Aminou, T «Characterization and application of alkali-soluble polysaccharide of Carica papaya seeds for removal of indigo carmine and Congo red dyes from single and binary solutions” JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING, 7, 5, 103343, OCT 2019, DOI: 10.1016/j.jece.2019.103343
11-Kermorgant, M. & al. «Evaluation of Upconverting nanoparticles towards heart theranostics” PLOS ONE, 14, 12, e0225729, DEC 2019, DOI: 10.1371/journal.pone.0225729 This reference constitutes a first publication describing the potential of our NIR small animal imager dedicated to UNCPs (in vivo imaging).
12-Santelli & al. « Multimodal Gadolinium Oxysulfide Nanoparticles for Bioimaging: A Comprehensive Biodistribution, Elimination and Toxicological study” ACTA BIOMATERIALIA, 108, 261-272, MAY 2020, DOI: 10.1016/j.actbio.2020.03.013. This publication demonstrates the safety of our UNCPs injected into rats.
13- Fatombi, JK ; Agani, I ; Osseni, SA ; Idohou, EA ; Neumeyer, D ; Verelst, M ; Mauricot, R ; Aminou, T « Influence of salts and humic acid on 2,4-dichlorophenoxyacetic acid removing from aqueous solution by peanut shell activated carbon” DESALINATION AND WATER TREATMENT, 189, 250-263, JUN 2020, DOI: 10.5004/dwt.2020.25597
14- Marques, ND ; Nassar, EJ ; Verelst, M ; Mauricot, R ; Brunckova, H ; Rocha, LA « Effect of ytterbium amount on LaNbO4:Tm3+,Yb3+ nanoparticles for bio-labelling applications” ADVANCES IN MEDICAL SCIENCES, 65, 2, 324-33, SEP 2020, DOI: 10.1016/j.advms.2020.06.001
15- Agani, I ; Fatombi, JK ; Osseni, SA ; Idohou, EA ; Neumeyer, D ; Verelst, M ; Mauricot, R ; Aminou, T «Removal of atrazine from aqueous solutions onto a magnetite/chitosan/activated carbon composite in a fixed-bed column system: optimization using response surface methodology” RSC ADVANCES, 10, 41588-41599, NOV 2020, DOI: 10.1039/d0ra07873e
16- Idohou, EA ; Fatombi, JK ; Osseni, SA ; Agani, I ; Neumeyer, D ; Verelst, M ; Mauricot, R ; Aminou, T «Preparation of activated carbon/chitosan/Carica papaya seeds composite for efficient adsorption of cationic dye from aqueous solution” SURFACES AND INTERFACES, 21, 100741, DEC 2020, DOI: 10.1016/j.surfin.2020.100741
17- Silveira, RM ; de Almeida, ER ; Ospina, CA ; de Castro, GR ; Verelst, M ; Martines, MAU «Tailoring pore structures and morphologies of highly ordered cubic mesoporous silica prepared in mild conditions: the effects of reaction parameters” JOURNAL OF THE AUSTRALIAN CERAMIC SOCIETY, 05 February 2021, DOI: 10.1007/s41779-021-00570-9
18- Santelli, J. & al. “Custom NIR Imaging of New Up-Conversion Multimodal Gadolinium Oxysulfide Nanoparticles” PARTICLE & PARTICLE SYSTEMS CHARACTERIZATION, April 202, 38, (4)
articipants: Magali Brunet, Christophe Faulmann, Philippe Sciau
Doctoral students: Minli Wang, Chenchen Luo, and Senwei Xia
This activity, developed by a multidisciplinary team (chemistry/physics) in close collaboration with archaeology and history laboratories (TRACES, FRAMESPA, ASM, CRCAO), lies at the crossroads of materials science, the history of technology, and archaeology.
More specifically, the team’s approach consists of studying archaeological or historical objects by focusing on the materials (composition, structures, and physical properties) that compose them. The results obtained are placed in their historical context and compared with historical and archaeological data.
The work carried out at CEMES consists of :
The team is currently studying two types of materials:
-Ancient ceramics-(Axis-1)
CEMES is a provider of access to the European research infrastructure for
heritage E-RIHS: Science (https://www.e-rihs.eu/). In this
context, the laboratory provides external users with several transmission
electron microscopes and a Dual Beam (FIB/SEM) dedicated to MET sample
preparation. The Heritage Materials team will provide its expertise in the
acquisition, processing, and interpretation of data concerning materials in
axes 1 and 2.
=> Consult the service catalog https://catalogue.e-rihs.eu/catalogue?q=cemes
Contact: Philippe Sciau
After studying the materials used in Greek and Roman pottery glazes by developing appropriate tools and methodologies, we have broadened our scope to include Chinese ceramic glazes. Collaborations have been established with French historians (FRAMESPA; https://framespa.univtlse2.fr/ and CRCAO http://www.crcao.fr/), Chinese archaeometric teams from Sun Yat-Sen University in Guangzhou, the University of the Chinese Academy of Sciences in Beijing, and currently with the Institute of Silicate Cultural Heritage at Shaanxi University of Science and Technology in Xi’an.
The main objective is to use a detailed study of the microstructure and physical properties of glazes and model systems synthesised in the laboratory to provide new insights into the manufacturing processes, their possible local characteristics and their evolution over time. Among other things, we are seeking to determine the compositions and formation conditions of the crystalline phases formed during firing (Figs. 1 and 2), depending on the nature (chemical and mineral) of the raw material used. As the colouring elements of the glazes studied are based on transition metals (Fe, Mn, Co, Cu), particular attention is paid to the crystals and glassy phases containing them. Their origin is also investigated: i) presence in the raw material, ii) addition in the form of more or less pure simple oxides, or iii) via a pigment of complex composition. The role of these transition elements, as well as that of glass phase demixing phenomena in colour, are also studied. The information deduced from these physicochemical data is then compared with historical data (archive studies) and archaeological data (excavations). This work also aims to provide information in the field of art authentication.
Theses defended:
• Clément Hole, Black and brown glazes of the Song dynasty: materials with high potential for science and heritage history, doctoral thesis from the University of Toulouse (2022). HAL Id: tel-04024035, version 1
• Ariane Pinto, Microstructure and technical processes of Ginghua porcelain: an approach through materials science, doctoral thesis, University of Toulouse (2019). HAL Id: tel-02736090, version I
• Tian Wang, Multi-scale study of ancient ceramics using a series of analytical techniques, doctoral thesis, University of Toulouse (2016). HAL Id: tel-02011149, version 1
Articles: https:/hal.science/search/index?q=Philippe+sciau
Figure 1: Schematic representation of dendrite growth on the glaze
Figure 2: Crystallographic study of a dendrite in a sauce glaze. Elemental mapping (CM20-EDX) and phase mapping (CM20-ASTAR). Haematite (yellow), pseudobrookite (green), ε-Fe2O3 (red) and spinel (blue).
Contact: Magali Brunet
This axis concerns the study of the first light alloys used in aeronautics, through an approach combining laboratory analysis and archival research. The study corpus consists of parts from vintage aircraft preserved and restored by associations such as Les Ailes Anciennes de Toulouse in Blagnac, or from crashed aircraft (mainly from the Second World War) whose exploration is managed by the Aerocherche association (Figure 1).
Figure 1. Fragment of the fuselage of a Dornier 217 (1943) from excavations carried out by the Aérocherche association – MET image of fine precipitates in the reinforced aluminium alloy; optical microscope image of the coating layers (primer/anti-corrosion paint).
The physical and chemical properties, the structure of the crystalline phases present and their arrangement/organisation at different scales are studied using a combination of various analytical techniques: electron microscopy (scanning SEM, transmission TEM) and associated spectroscopies (EDX, EELS), Raman spectroscopy, and X-ray diffraction/diffraction methods. The analyses cover both healthy metal and altered metal, as well as coatings (primers, paints).
Through these analyses, we aim to:
– From a fundamental perspective, deepen our understanding of the physical mechanisms involved in the ageing of materials and the relationships between material, function and properties in these heterogeneous and complex environments.
– Establish a link between the physical and chemical nature of alloys, exposure conditions and the type of alterations observed. This information is essential for developing practical methods of conservation and restoration at the object level: in this case, preventing aircraft corrosion.
– Document the materials and their manufacturing methods and, from a historical perspective, reveal the evolution of aluminium alloys during a period when the aeronautical industry underwent significant development. Testimonials from volunteers, archives, industrial technical documents and other scientific articles from the period provide valuable information on the history of aircraft and the materials they are made of.
Theses defended:
• Audrey Cochard, Microstructures and mechanical properties of duralumin-type alloys from the Breguet 765 No. 5004 64-PH, historical approach and materials science. Doctoral thesis from the University of Toulouse (2016). Co-supervision: CEMES-CNRS (Ph. Sciau) / FRAMESPA – University of Toulouse Jean-Jaurès (J.M. Olivier)
• Toufa Ouissi, Study of the first duralumin-type aeronautical alloys used in military aviation between 1930 and 1945. Historical approach and materials science. Doctoral thesis from the University of Toulouse (2016). Co-supervision: CEMES-CNRS (Ph. Sciau) / FRAMESPA – University of Toulouse Jean-Jaurès (J.M. Olivier)
• Agathe Duclos, Relationships between the microstructure and mechanical properties of old aluminium alloys from Second World War aircraft, doctoral thesis University of Toulouse (2025), co-supervised by CEMES-CNRS (M. Brunet) / CIRIMAT-INP (B. Malard).
Past and present projects:
• STELAIR (2016-2019) – EUR NanoX Project
Title: Aging Studies of aluminium alloys Encountered in old Aircrafts
Coordinator: CEMES – M3 group; Partners: CEMES – PPM group; CIRIMAT – ENSIACET
Subject: Long-term ageing of Al-Cu alloys, based on the examination of materials from old aircraft. Various laboratory analyses were used to characterise the composition and nanostructure of the selected, naturally aged alloys (Figure 2). The aim was to determine the structural evolution of light alloys over very long periods and the correlation with their mechanical behaviour.
Figure 2. a) Bright field STEM image of precipitates in a duralumin alloy (1958) in the [112]Al zone axis showing θ’-Al2Cu platelets (black arrows) and Ω-Al2Cu platelets (white arrows) growing on the dispersoids (AlMnSi); b) STEM-HAADF image of the Ω-Al2Cu precipitate (Images UMS Centre Raimond Castaing).
• PROCRAFT (2020-2023) – European JPI-CH Project; https://grand-patrimoine.loireatlantique.fr/jcms/navigation/les-services/arc-antique/projet-procraft-fr-p2_324372
Title: Protection and Conservation of Heritage Aircraft.
Coordinator: Arc Antiques (Nantes); Partners: CEMES; TRACES; University of Bologna (Italy); University of Ferrara (Italy); CTU (Czech Republic) – Associated partners: Museums, associations, local authorities.
Subject: The main objective of the project was to propose procedures and solutions for each key stage in the conservation of heritage aeronautical objects (mainly aircraft from the Second World War): conservation-restoration, development of coatings for outdoor protection, preventive conservation solutions for hangar-type environments, and procedures for non-professionals involved in this type of heritage (typically associations). The project has provided a better understanding of the technologies (metallurgy and aluminium coatings) of that period, improved conservation and enabled dissemination and presentation to the public.
• PaerO Project (2022-2025) funded by the key challenge ‘Sciences of the Past in Occitania’.
Website: https://sciencesdupasse.univ-toulouse.fr/projet-paero/
Title: Aerospace Heritage — aircraft crashes (sites and remains) from 1927 & 1945 in Occitanie.
Coordinator: CEMES; Partners: FRAMESPA-UT2J; CIRIMAT-INP; Association Aérocherche; Aeroscopia Museum; Haute-Garonne Departmental Archives
Subject: The aim of the project was to retrace, through crash sites and the analysis of material evidence, a few pages of Occitanie’s aeronautical history, from the beginnings of the Aeropostale (late 1910s) to the end of the Second World War. The methodology employed was interdisciplinary, combining the humanities and the hard sciences. This precious heritage from archaeological excavations has been widely disseminated and promoted to the public: in research (seminars), to the general public (travelling exhibition ‘Memories of the Air’) and to schools (educational game).
• CATCH Project (2025-2026) – International Emerging Action CNRS
Title: Study of ChromAte-based pigmenTs in Cultural HeritageInternational collaboration between CEMES-CNRS and SCITEC-CNR (Perugia, Italy)
Subject: The project aims to identify the constituents of a historic anti-corrosion paint (primer), in particular zinc chromate-based pigments. These chromates are resynthesised using procedures based on patents from the 1940s, then characterised in the laboratory (XRD, Raman, microscopy) and by synchrotron techniques (XRD). The primers synthesised in the laboratory can then be compared with those found on historic aircraft parts. The aim is also to assess whether the properties of these chromates are preserved after long-term ageing. X-ray absorption spectroscopy (XAS) is used because it is a powerful technique for probing interfaces at the (sub)micrometric scale and for obtaining information on oxidation changes in elements such as chromium (Figure 3).
Figure 3. On a fragment of a Heinkel 111 aircraft (Germany, 1937) covered with a primer coat and several layers of paint (grey, green): XANES spectra around the chromium threshold, acquired on the LUCIA line, SOLEIL synchrotron, through the interface. a) In the area where the primer/paint layer is preserved, the spectra are close to a Cr(VI) spectrum, and b) in the area where the protection is absent and has been replaced by earthy concretions, the spectra indicate the presence of Cr(III), linked to the reduction of chromates [Brunet 2022].
=> Articles: https://hal.science/search/index?q=magali+brunet
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